EP0497187B1 - Composition inhibitrice de dépôt pour réacteur de polymérisation et méthode pour polymériser des monomères vinyliques utilisant celle-ci - Google Patents

Composition inhibitrice de dépôt pour réacteur de polymérisation et méthode pour polymériser des monomères vinyliques utilisant celle-ci Download PDF

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Publication number
EP0497187B1
EP0497187B1 EP92100912A EP92100912A EP0497187B1 EP 0497187 B1 EP0497187 B1 EP 0497187B1 EP 92100912 A EP92100912 A EP 92100912A EP 92100912 A EP92100912 A EP 92100912A EP 0497187 B1 EP0497187 B1 EP 0497187B1
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EP
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Prior art keywords
polyhydric phenol
polymerization
vinyl
deposit
suppressant composition
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EP92100912A
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German (de)
English (en)
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EP0497187A1 (fr
Inventor
Takeshi Sumino
Tetsuyoshi Yano
Masayuki Murashige
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Sumitomo Chemical Co Ltd
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Sumitomo Chemical Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/002—Scale prevention in a polymerisation reactor or its auxiliary parts
    • C08F2/004—Scale prevention in a polymerisation reactor or its auxiliary parts by a prior coating on the reactor walls
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F14/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
    • C08F14/02—Monomers containing chlorine
    • C08F14/04—Monomers containing two carbon atoms

Definitions

  • the present invention relates to a deposit suppressant composition for the internal surfaces of a vinyl-polymerization reactor and a method of polymerizing vinyl monomers with use of said deposit suppressant composition.
  • a problem with the polymerization of vinyl monomers is a progressive deposit on the internal surfaces of a polymerization reactor, more specifically on the internal wall of the reactor and the surfaces of the impeller, baffles and so on.
  • a deposit on the internal surfaces of a polymerization reactor not only detract from the reactor cooling efficiency but, on detachment of the deposit and entry of the deposit into the product polymer, adversely affect the quality of the product polymer. Furthermore, much labor and time are required for removal of the deposit after the polymerization reaction. Therefore, more than a few methods comprising application of build-up suppressants have heretofore been proposed.
  • Japanese Examined Patent Publication (Kokoku) No. 30343/1970 teaches the use of polar organic compounds such as thioethers.
  • Japanese Examined Patent Publication No. 363/1990 discloses condensates of phenolic compounds with formaldehyde or benzaldehyde.
  • Japanese Unexamined Patent Publication (Kokai) No. 34241/1989 discloses a reaction product of a thiodiphenol and a bleaching agent.
  • US-A-4 555 555 describes condensates of pyrogallol or hydroxyhydroquinone with aromatic aldehydes.
  • US-A-4 431 783 teaches a 1-naphthol-formaldehyde condensate.
  • Japanese Unexamined Patent Publication No. 132907/1987 teaches polysulfide rubbers.
  • the present invention provides a deposit suppressant composition for the internal surfaces of a polymerization reactor for polymerizing vinyl monomers, which comprises a polyhydric phenol sulfide compound having an average molecular weight of 500 to 5000.
  • the present invention further provides a method of polymerizing vinyl monomers wherein prior to the polymerization, the internal surfaces of a polymerization reactor are coated with a deposit suppressant composition and then the polymerization is carried out, the method being characterized in that the deposit suppressant composition comprises a polyhydric phenol sulfide compound having an average molecular weight of 500 to 5000.
  • the polyhydric phenol constituting the polyhydric phenol sulfide compound mentioned above is a phenol compound having two or three -OH groups and may have substituents such as hydrocarbon groups of 1 to 3 carbon atoms, particularly alkyl groups, or halogens on the aromatic ring thereof.
  • Preferred examples of such polyhydric phenol compounds are resorcinol, hydroquinone, catechol, hydroxyhydroquinone, pyrogallol, phloroglucinol and so on.
  • the average number of polyhydric phenol units is about 4 to 30, preferably about 8 to 15, and the polyhydric phenol units may be the same or different.
  • the number of intervening sulfur atoms between adjacent polyhydric phenols is 1 to 8 on the average.
  • the average molecular weight as determined by gel permeation chromatography (GPC) based on standard polystyrene is 500 to 5000, preferably about 800 to 3000.
  • the average molecular weight herein is indicated in terms of weight average molecular weight. If the molecular weight is less than the above range, the deposit suppressant effect will not be sufficient, nor will it last long, while an excessive molecular weight tends to make the coating operation difficult.
  • An exemplary process comprises condensing said polyhydric phenol compound with sulfur monochloride. It is required that the polyhydric phenol sulfide compound be obtainable by this exemplary process when the designated state is Germany, France or Great Britain.
  • a polyhydric phenol is first dissolved in an organic solvent inert to sulfur monochloride.
  • the organic solvent mentioned just above includes aromatic hydrocarbons such as toluene, xylene, chlorobenzene, ethylene dichloride, chloroform, and ethyl acetate. Then, sulfur monochloride is slowly added to the solution with heating and stirring.
  • the amount of sulfur monochloride to be used is 0.5 to 2 moles, preferably about 0.9 to 1.2 moles, per mole of the polyhydric phenol.
  • the reaction temperature may range from 50°C to 150°C, preferably about 80°C to about 120°C.
  • reaction time may generally range from 0.5 to 5 hours.
  • the byproduct hydrogen chloride formed with the progress of reaction may be let off under atmospheric pressure.
  • a suitable hydrochloric acid acceptor such as triethylamine can be employed.
  • reaction product if present in solution, can be recovered by evaporating the solvent. If the reaction product has precipitated out in the reaction mixture, it can be isolated by a solid-liquid separation technique, for example by filtration.
  • the polyhydric phenol sulfide compound is dissolved in a solvent. That is to say, the deposit suppressant composition of the invention is usually in the form of a solution of the polyhydric phenol sulfide compound in a solvent capable of dissolving the polyhydric phenol sulfide compound.
  • the solvent mentioned above is preferably a solvent that can be easily evaporated and is capable of dissolving the polyhydric phenol sulfide compound.
  • solvent include various organic solvents such as lower alcohols, particularly C1-C4 saturated aliphatic alcohols, e.g. methanol, ethanol, etc.; various ketones, particularly di(C1-C4 alkyl) ketones, e.g.
  • aqueous alkali solutions aqueous solutions of alkali metal hydroxide such as NaOH or KOH, etc. can be mentioned, and the preferred concentrations of such aqueous solutions are about 0.5 to 10 percent by weight.
  • the concentration of the polyhydric phenol sulfide compound in the final deposit suppressant solution is not critical so far as the solution is suited for coating purposes, and generally may range from about 0.001 to about 50 g per 100 ml of the solvent.
  • internal surfaces of a polymerization reactor used herein is intended to mean all the surfaces that will come into contact with the charged monomer, such as the surfaces of the internal wall, impeller shaft, blades and baffles, and the inner surfaces of the reflux condenser and conduits.
  • the material or materials constituting such internal surfaces need not be extraordinary but may be any of the conventional materials, such as stainless steel or glass, for all practical purposes.
  • the method for application of the deposit suppressant composition of the invention to the internal surfaces of a polymerization reactor is not critical as long as the surfaces can be adequately coated.
  • Well-known methods can be used, such as spraying the internal surfaces of the reactor with the composition or filling the reactor with the composition and withdrawing the composition.
  • any of the known automatic coating methods as described in Japanese Unexamined Patent Publications No. 61001/1982, No. 36288/1980 and No. 11303/1984, for instance, can be utilized.
  • the amount of the deposit suppressant composition to be applied to the internal surfaces of a polymerization reactor is 0.01 to 10 g/m2 in terms of the polyhydric phenol sulfide compound. If the amount is less than 0.01 g/m2, the deposit suppressant effect will be inadequate and will not last long. The use of the composition in an amount of more than 10 g/m2 will not achieve further remarkable improvement in the desired effect.
  • the above coating of internal surfaces of the polymerization reactor with the deposit suppressant composition of the invention is performed prior to polymerization of the vinyl monomer.
  • the coating operation can be carried out before every batch reaction but since the deposit suppressant effect of the composition is remarkable, several batches of reaction can be consecutively conducted after each coating operation and, after checking for the degree of deposition, another coating procedure can be carried out.
  • the optimal next coating time can be determined by monitoring the degree of the deposit, for example, from heat exchange efficiency.
  • the polymerization methods to which the deposit suppressant composition of the invention can be applied are suspension polymerization, emulsion polymerization, microsuspension polymerization, solution polymerization, bulk polymerization, gas-phase polymerization and so on, all of which are well known.
  • the effect of the invention is particularly remarkable in suspension, emulsion or microsuspension polymerization in an aqueous medium.
  • the typical vinyl monomers which can preferably be polymerized in accordance with the invention are vinyl halides such as vinyl chloride; vinyl esters such as vinyl acetate, vinyl propionate, etc., alkyl (meth)acrylates such as methyl methacrylate; esters, particularly lower alkyl esters of unsaturated dibasic acids such as maleic acid, fumaric acid, etc.; diene monomers such as butadiene, chloroprene, isoprene, etc.; styrene, acrylonitrile, vinylidene halides, vinyl ethers and so on.
  • vinyl halides such as vinyl chloride
  • vinyl esters such as vinyl acetate, vinyl propionate, etc.
  • alkyl (meth)acrylates such as methyl methacrylate
  • esters, particularly lower alkyl esters of unsaturated dibasic acids such as maleic acid, fumaric acid, etc.
  • diene monomers such as butadiene, chloropren
  • These monomers can be used alone or in combination where copolymerizable, and may also be used in combination with, inter alia , acrylic acid, methacrylic acid, maleic acid or fumaric acid or the corresponding anhydrides thereof, itaconic acid, acrylamide, methacrylamide, dimethylaminoethyl methacrylate, N-methylolacrylamide, N-methylolmethacrylamide, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, acrolein, C2-C9 olefins such as ethylene, propylene, and so on.
  • the deposit suppressant composition of the invention is particularly suited for the suppression of deposit formation in polymerizing vinyl chloride or a vinyl monomer mixture containing vinyl chloride as a major component and other monomer(s) copolymerizable therewith as a minor component.
  • Such mixture preferably contains at least 50 wt%, preferably more than 80 wt% but less than 100 wt%, of vinyl chloride.
  • Examples of other monomers copolymerizable with vinyl chloride are any of the above-exemplified vinyl monomers which are copolymerizable with vinyl chloride, and particularly include vinyl acetate, alkyl (meth)acrylate, especially C1-C6 alkyl (meth)acrylate, and the like.
  • the deposit suppressant composition of the invention is also applicable to graft-copolymerization process wherein vinyl chloride is graft-copolymerized to an ethylene-vinyl acetate copolymer, ethylene-alkyl methacrylate copolymer, poly urethane and the like.
  • the polymerization initiator, the dispersing agent for use in combination with an aqueous medium, etc. may all be well-known conventional reagents, and there is no specific restriction on the polymerization temperature, time and other conditions.
  • a suspension polymerization of a vinyl monomer can be carried out in a conventional manner in an aqueous medium such as water using a conventional dispersant (such as partially saponified polyvinyl acetate, carboxymethyl cellulose, gelatin, starch or like water-soluble macromolecular compounds) and, if desired, an auxiliary dispersion stabilizer (such as barium sulfate or the like) and using a conventional oil-soluble initiator such as benzoyl peroxide, lauroyl peroxide, 2,2'-azobisisobutyronitrile, di-2-ethylhexyl peroxydicarbonate or the like, at a temperature effective to effect the polymerization (usually about 20 to 80°C) with stirring until the desired polymer is obtained.
  • a conventional dispersant such as partially saponified polyvinyl acetate, carboxymethyl cellulose, gelatin, starch or like water-soluble macromolecular compounds
  • an auxiliary dispersion stabilizer such as barium
  • the emulsion polymerization is also carried out in a conventional manner in an aqueous medium such as water using a conventional emulsifier (such as a salt of a sulfuric acid ester of a higher alcohol, alkylsulfonic acid salts or similar anionic surfactants or polyoxyethylene alkyl ethers or similar nonionic surfactants) and using conventional water-soluble initiators (such as hydrogen peroxide, potassium persulfate, ammonium persulfate or a redox catalyst) at a temperature of about 20 to 80°C, with stirring until the desired polymer is obtained.
  • a conventional emulsifier such as a salt of a sulfuric acid ester of a higher alcohol, alkylsulfonic acid salts or similar anionic surfactants or polyoxyethylene alkyl ethers or similar nonionic surfactants
  • conventional water-soluble initiators such as hydrogen peroxide, potassium persulfate, ammonium persulfate or a redox catalyst
  • the microsuspension polymerization can also be carried out in a conventional manner in an aqueous medium using a conventional emulsifier and an oil-soluble initiator such as one mentioned above.
  • the reaction system is homogenized prior to the initiation of the polymerization.
  • the polymerization is effected at a temperature of, for example, about 20 to about 80°C with stirring until the desired polymer is obtained.
  • Such polymerization method is described, for example, in "Encyclopedia of PVC", 1976, edited by LEONARD I. NASS, MARCEL DEKKER, INC., New York, pages 88-89.
  • the polyhydric phenol sulfide compound of the invention exhibits a very remarkable deposit suppressant effect when applied to the internal surfaces of a polymerization reactor for vinyl monomers. It is particularly suited for the polymerization of vinyl chloride or the like in aqueous phase. When the reactor body, impeller blades and so on are made of stainless steel, the surfaces of these members are generally finished mirror-smooth by electrolytic polishing.
  • the polyhydric phenol sulfide compounds of the invention adhere well to such surfaces and exhibit the deposit suppressant effect for a long period of time.
  • a three-necked flask equipped with a reflux condenser and a stirrer was charged with 25 g (0.2 mole) of pyrogallol and 80 ml of ethyl acetate and heated with stirring to a temperature at which reflux of ethyl acetate took place. Then, 18 ml (0.2 mole) of sulfur monochloride was added dropwise over a period of 2 hours at the same temperature. After completion of the dropwise addition, the solvent was evaporated to give a pyrogallol sulfide. The obtained sulfide compound was heated at 120°C for a period of 5 hours.
  • the molecular weight of the sulfide compound as determined by GPC was 2330 based on standard polystyrene.
  • the average number of pyrogallol units is estimated to be about 12
  • the average number of intervening sulfur atoms between the adjacent pyrogallol units is estimated to be about 2.
  • Example 2 The procedure of Example 1 was repeated except that 24 g (0.22 mole) of resorcinol was used in lieu of pyrogallol to give a resorcinol sulfide.
  • the molecular weight of the sulfide compound was 1190 on the same basis as above.
  • the average number of resorcinol units is estimated to be about 7
  • the average number of intervening sulfur atoms between the adjacent resorcinol units is estimated to be about 2.
  • the polyhydric phenol sulfide prepared in Examples 1 and 2 were respectively dissolved in methanol to give two different deposit suppressant compositions each containing the sulfide compound in an amount of 0.1 g per 100 ml of methanol.
  • Example 3 Three test pieces of electrolytically polished stainless steel plate SUS 316L, 5 cm x 15 cm each, were provided, and two of them were spray-coated with the above respective two deposit suppressant compositions in an amount of 0.15 g/m2 calculated as solids to form a coating film (Examples 3 and 4). The remaining one test piece was used as uncoated (Comparative Example 1).
  • test pieces were installed within a glass-lined polymerization reactor of 100-liter capacity at the level about one-third up from the bottom.
  • the polymerization reactor was charged with 40 kg of deionized water, 25 kg of vinyl chloride, 150 g of sodium lauryl sulfate, 100 g of stearyl alcohol and 4.0 g of di-2-ethylhexyl peroxydicarbonate.
  • the polyhydric phenol sulfide prepared in Example 1 was dissolved in methanol to provide a deposit suppressant composition containing 0.1 g of the sulfide compound per 100 ml of methanol.
  • the internal wall and other parts of a glass-lined polymerization reactor of 100-liter capacity which were to be exposed to the monomer charge were spray-coated with the above deposit suppressant composition in an amount of 0.1 g/m2 calculated as solids to form a coating film.
  • the contents were withdrawn and the interior of the reactor was gently rinsed with water. Then, the deposits were scraped off from the internal surfaces which had been exposed to the liquid phase. The amount of deposits was 180 g/m2. There was no abnormality in the particle size or color of the product polymer.
  • Example 5 The procedure of Example 5 was repeated except that the reactor was not coated with the deposit suppressant composition.
  • the amount of deposits formed on the internal surfaces which had been exposed to the liquid phase was as large as 1090 g/m2.
  • the internal wall and other parts of a stainless steel polymerization reactor of 10-liter capacity which were to be exposed to the monomer charge were spray-coated with a deposit suppressant composition of Example 1 in an amount of 0.3 g/m2 calculated as solids to form a film.
  • This polymerization reactor was charged with 4 kg of deionized water, 1.7 g of partially saponified polyvinyl acetate with a saponification degree of 80% and a viscosity of 48 cps (4% in water, at 20°C) and 0.74 g of di-2-ethylhexyl peroxydicarbonate. After purging, the reactor was charged with 3 kg of vinyl chloride monomer and the polymerization reaction was conducted at 57°C with stirring. When the internal pressure of the reactor had fallen by 1.5 kg/cm2, the unreacted monomer was dispelled out to terminate the reaction and the contents were withdrawn. There was no deposit on the internal surfaces of the polymerization reactor.
  • Example 6 The procedure of Example 6 was repeated except that the internal surfaces of the polymerization reactor was not coated with any deposit suppressant composition.
  • the amount of deposits formed on the internal surfaces which had been exposed to the liquid phase was 103 g/m2 in this case.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polymerisation Methods In General (AREA)

Claims (9)

  1. Composition inhibitrice de dépôt pour les surfaces internes d'un réacteur de polymérisation destiné à la polymérisation d'un monomère vinylique, comprenant un composé de sulfure de phénol polyvalent ayant un poids moléculaire moyen de 500 à 5000, que l'on obtient par condensation d'un composé de phénol polyvalent avec du monochlorure de soufre.
  2. Composition inhibitrice de dépôt selon la revendication 1, dans laquelle ledit sulfure de phénol polyvalent comprend des fractions de phénol polyvalent avec au moins un membre choisi parmi le résorcinol, l'hydroquinone, le catéchol, l'hydroxyhydroquinone, le pyrogallol et le phloroglucinol.
  3. Composition inhibitrice de dépôt selon la revendication 2, dans laquelle ladite fraction de phénol polyvalent est le pyrogallol.
  4. Composition inhibitrice de dépôt selon l'une quelconque des revendications 1 à 3, dans laquelle ledit monomère vinylique est le chlorure de vinyle ou un mélange de monomères contenant du chlorure de vinyle comme composant majeur et un ou plusieurs autres monomères vinyliques copolymérisables avec le chlorure de vinyle.
  5. Composition inhibitrice de dépôt selon l'une quelconque des revendications 1 à 4, dans laquelle on condense un composé de phénol polyvalent avec du monochlorure de soufre à une température de 50 à 150°C pendant un laps de temps de 0,5 à 5 heures, le monochlorure de soufre étant utilisé en une quantité de 0,5 à 2 moles par mole du composé de phénol polyvalent.
  6. Procédé de polymérisation d'un monomère vinylique, dans lequel, avant la polymérisation, on enduit les surfaces internes d'un réacteur de polymérisation destiné à la polymérisation d'un monomère vinylique avec une composition inhibitrice de dépôt, et ensuite on procède à la polymérisation, le procédé étant caractérisé en ce que la composition inhibitrice de dépôt comprend un composé de sulfure de phénol polyvalent selon l'une quelconque des revendications 1, 2, 3 et 5.
  7. Procédé de polymérisation d'un monomère vinylique selon la revendication 6, dans lequel ledit monomère vinylique est le chlorure de vinyle ou un mélange de monomères contenant du chlorure de vinyle comme composant majeur et un ou plusieurs autres monomères vinyliques copolymérisables avec le chlorure de vinyle.
  8. Procédé de polymérisation d'un monomère vinylique selon la revendication 6 ou 7, dans lequel on applique ladite composition inhibitrice de dépôt sur lesdites surfaces internes en une quantité de 0,01 à 10 g/m² calculée comme ledit composé de sulfure de phénol polyvalent.
  9. Utilisation d'un composé de sulfure de phénol polyvalent tel que défini dans l'une quelconque des revendications 1, 2, 3 et 5, pour inhiber les dépôts sur les surfaces internes d'un réacteur destiné à la polymérisation de monomères vinyliques.
EP92100912A 1991-01-30 1992-01-21 Composition inhibitrice de dépôt pour réacteur de polymérisation et méthode pour polymériser des monomères vinyliques utilisant celle-ci Expired - Lifetime EP0497187B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP3009677A JP3057520B2 (ja) 1991-01-30 1991-01-30 フェノール類のスルフィド化合物を主成分とする重合器内部表面の付着防止剤及び該付着防止剤を用いたビニル系単量体の重合方法
JP9677/91 1991-01-30

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EP0497187A1 EP0497187A1 (fr) 1992-08-05
EP0497187B1 true EP0497187B1 (fr) 1995-04-05

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US (1) US6156853A (fr)
EP (1) EP0497187B1 (fr)
JP (1) JP3057520B2 (fr)
KR (1) KR100187694B1 (fr)
DE (1) DE69201884T2 (fr)

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4555555A (en) * 1981-05-22 1985-11-26 Kanegafuchi Kagaku Kogyo Kabushiki Kaisha Process for polymerizing vinyl chloride with a scale prevention compound coated on a reaction surface

Family Cites Families (7)

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Publication number Priority date Publication date Assignee Title
US4228130A (en) * 1978-10-23 1980-10-14 The B. F. Goodrich Company Coating polymerization reactors with oligomers derived from polyhydric phenols plus a bleach
US4200712A (en) * 1978-10-23 1980-04-29 The B. F. Goodrich Company Coating polymerization reactors with oligomer coatings derived from reaction products of substituted phenols
CA1147098A (fr) * 1979-04-30 1983-05-24 Louis Cohen Revetement de reacteurs de polymerisation a l'aide des produits de reaction de thiodiphenols et d'un agent de blanchiment
DE3175656D1 (en) * 1980-10-31 1987-01-15 Ici Plc Vinyl chloride polymerisation process
JPS62132907A (ja) * 1985-12-05 1987-06-16 Mitsui Toatsu Chem Inc 塩化ビニルの重合方法
JPH02363A (ja) * 1988-12-23 1990-01-05 Hitachi Ltd 光電変換装置
JP2831412B2 (ja) * 1989-12-28 1998-12-02 三井化学株式会社 塩化ビニルの重合方法

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4555555A (en) * 1981-05-22 1985-11-26 Kanegafuchi Kagaku Kogyo Kabushiki Kaisha Process for polymerizing vinyl chloride with a scale prevention compound coated on a reaction surface

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Publication number Publication date
EP0497187A1 (fr) 1992-08-05
DE69201884T2 (de) 1995-09-21
JPH04339801A (ja) 1992-11-26
KR920014834A (ko) 1992-08-25
US6156853A (en) 2000-12-05
DE69201884D1 (de) 1995-05-11
KR100187694B1 (ko) 1999-06-01
JP3057520B2 (ja) 2000-06-26

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